The present invention provides a process for producing 1-acetyl-3,3-dimethylcyclohexane derivatives having the generic structure: ##STR3## wherein R.sub.1 or both of R.sub.2 and/or R.sub.3 is allyl or methallyl and the other of R.sub.1 or R.sub.2 and/or R.sub.3 is hydrogen by reaction of an allyl or methallyl halide with acetyl-3,3-dimethylcyclohexane. The 1-acetyl-3,3-dimethylcyclohexane derivatives are useful for their organoleptic properties in perfumes, perfumed articles, foodstuffs, chewing gums, medicinal products, tobaccos and tabacco articles.
In the perfumery art there is a considerable need for substituents having sweet, earthy, animal, green, herbaceous, melony and fruity aromas with pineapple, ambery, galbanum-like, ginger-like and citrusy nuances and tobacco/animal notes. Specifically described are materials having such a profile but which do not discolor with age. Such fragrance materials have a wide utilization in perfume formulations and perfumed articles. A minimum amount of such materials that give rise to these properties is available from natural sources, but the natural materials are subject to wide variations in quality, are expensive and are limited or often in critically short supply.
Furthermore, there is a continuing search for compositions which can vary, modify, fortify, enhance, augment or otherwise improve the flavor and aroma of foodstuffs, chewing gums and medicinal products. To be satisfactory, such compositions should be stable, non-toxic and blendable with other ingredients to provide its own unique flavor and aroma nuance without detracting from the co-ingredients. Preferably, such compositions should be naturally occurring or present in natural foodstuffs so that their ingestible safety can be readily recognized or similar to those materials present in natural foodstuffs so that their ingestible safety can be recognized. These materials should be capable of being synthesized in a simple and economical manner. The need for safe flavors in the fruity flavor area, e.g. citrus flavor area, is well-known, particularly in the beverage flavor area and in the yogurt flavor area. More specifically, there is a need for the development of non-toxic materials which can replace natural materials not readily available, having pineapple, allyl caproate-like, galbanum, woody, fatty, sweet, fruity, citrus, green and vegetable aroma characteristics and rosey, ionone-like, oriental-like, woody, sweet, fruity, and citrus flavor characteristics.
Firmenich's Dutch published application 7500838 discloses the preparation of the compound having the structure: ##STR4## and discloses its use in perfumery and in augmenting foodstuff flavors. The perfumery use of this compound and other members of its class as "floral, green, herbaceous and chypre" useful in galbanum resinoids is also disclosed.
The compounds disclosed in Dutch publised application 7500838 have organoleptic properties which cause them to be different in kind from the 1-acetyl-3,3-dimethylcyclohexane derivatives of our invention, which have unobvious, unexpected and advantageous characteristics in the field of augmenting or enhancing the organoleptic impressions of foodstuffs, foodstuff flavors, chewing gums, perfumes, perfumed articles, medicinal products, tobacco and tobacco flavors.
Insofar as relevant prior art concerning the process for preparing 1-acetyl-3,3-dimethylcyclohexane derivatives is concerned, German Pat. No. 1,244,784 issued on July 20, 1967, discloses the reaction: ##STR5## wherein R" can be one of alkyl, alkenyl, allyl, propargyl, cyclohexyl or benzyl; X is chloro or bromo and R.sub.1 ", R.sub.2 ", R.sub.3 ", R.sub.4 " and R.sub.5 " can be hydrogen, alkyl, alkenyl or phenyl. The reaction of the German Patent is limited to ketones. However, the nature of the reaction is different in kind from the reaction of the instant invention.
German Pat. No. 1,244,784 corresponds to British Pat. No. 1,059,839 published on Feb. 22, 1967, entitled, "Process for Preparing Ketones and Novel Ketones so Prepared." Tamai, et al, U.S. Pat. No. 3,983,175 issued on Sept. 28, 1976, (a continuation-in-part of Ser. No. 417,201 filed on Nov. 19, 1973, now abandoned) discloses a process for producing substituted ketones by reacting an organic halide with a ketone which has a replaceable hydrogen atom on the carbon atom in the alpha position to the carbonyl group in the presence of an aqueous alkali metal hydroxide and a nitrogen-containing base as a catalyst, e.g., primary amines, secondary amines, tertiary amines, and quarternary ammonium salts. The nature of the reaction described in the patent by Tamai, et al, is different in kind from the reaction of the instant invention. The same holds true for Meuly, et al, U.S. Pat. 3,668,255 issued on June 6, 1972, a continuation-in-part of Ser. No. 241,036, filed Nov. 29, 1962, now abandoned.